Semiconductor constructions having crystalline dielectric layers

ABSTRACT

The invention includes methods of forming capacitors and capacitor constructions. In one implementation, a method of forming a capacitor includes forming a first capacitor electrode. A first layer of a first capacitor dielectric material is formed over the first capacitor electrode. A second layer of the first capacitor dielectric material is formed on the first layer. A second capacitor electrode is formed over the second layer of the first capacitor dielectric material. A capacitor in accordance with an implementation of the invention includes a pair of capacitor electrodes having capacitor dielectric material therebetween comprising a composite of two immediately juxtaposed and contacting, yet discrete, layers of the same capacitor dielectric material.

TECHNICAL FIELD

This invention relates to capacitors and to methods of formingcapacitors.

BACKGROUND OF THE INVENTION

Typical capacitors comprise a pair of conductive electrodes spaced apartby intervening capacitor dielectric material. As integrated circuitrybecomes denser and as individual electronic components such ascapacitors get smaller, integrated circuitry fabricators face thechallenge of developing capacitor constructions and materials whichachieve desired capacitance despite the decreasing size. Examplematerials under consideration for capacitor dielectric layers includetitanates and tantalum pentoxide. These and other capacitor dielectriclayer materials can occur in crystalline and in amorphous phases.

It is generally known that the capacitance of dielectric materials suchas these can, at least initially, be increased from their as-depositedform by annealing. Such annealing can promote crystallization,re-crystallization or crystal realignment which can facilitate increasein capacitance and reduction in current leakage through the material.However, such annealing can also cause single crystals to be formed inthe dielectric layer which in essence extend entirely through thedielectric layer between the layer's opposing surfaces. Annealing orcrystal formation to this degree can undesirably have the effect ofincreasing current leakage. This is primarily due to continuous pathsbeing provided by the continuous grain boundaries for current leakagefrom one side of the layer to the other. It would be desirable toimprove upon these adverse characteristics of capacitor dielectric layermaterials.

SUMMARY OF THE INVENTION

The invention in one aspect includes methods of forming capacitors andto capacitor constructions. In one implementation, a method of forming acapacitor includes forming a first capacitor electrode. A first layer ofa first capacitor dielectric material is formed over the first capacitorelectrode. A second layer of the first capacitor dielectric material isformed on the first layer. A second capacitor electrode is formed overthe second layer of the first capacitor dielectric material. Inaccordance with another implementation, the first layer comprises afirst titanate compound comprising capacitor dielectric material and thesecond layer comprises a different second titanate compound comprisingcapacitor dielectric material. A capacitor in accordance with animplementation of the invention includes a pair of capacitor electrodeshaving capacitor dielectric material therebetween comprising a compositeof two immediately juxtaposed and contacting, yet discrete, layers ofthe same capacitor dielectric material. A capacitor in accordance withanother implementation includes a pair of capacitor electrodes havingcapacitor dielectric material therebetween comprising a composite of twoimmediately juxtaposed and contacting, yet discrete, layers of twodifferent capacitor dielectric materials, said two capacitor dielectricmaterials including two different titanate compounds. A capacitor inaccordance with still another implementation includes a pair ofcapacitor electrodes having capacitor dielectric material therebetweencomprising a composite of two immediately juxtaposed and contacting, yetdiscrete, layers of two different capacitor dielectric materials, one ofthe two different materials comprising a titanate compound and the othercomprising Ta₂O₅.

BRIEF DESCRIPTION OF THE DRAWINGS

Preferred embodiments of the invention are described below withreference to the following accompanying drawings.

FIG. 1 is a diagrammatic sectional view of a wafer fragment at oneprocessing step in accordance with the invention.

FIG. 2 is a view of the FIG. 1 wafer fragment at a step subsequent tothat shown by FIG. 1.

FIG. 3 is a view of the FIG. 1 wafer at a processing step subsequent tothat shown by FIG. 2.

FIG. 4 is a view of the FIG. 1 wafer at a processing step subsequent tothat shown by FIG. 3.

FIG. 5 is a view of the FIG. 1 wafer at a processing step subsequent tothat shown by FIG. 4.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

This disclosure of the invention is submitted in furtherance of theconstitutional purposes of the U.S. Patent Laws “to promote the progressof science and useful arts” (Article 1, Section 8).

A semiconductor wafer in process in accordance with one aspect of theinvention is indicated in FIG. 1 with reference numeral 10. Suchcomprises a semiconductive substrate in the form of a bulkmonocrystalline silicon substrate 12. In the context of this document,the term “semiconductive substrate” is defined to mean any constructioncomprising semiconductive material, including, but not limited to, bulksemiconductive materials such as a semiconductive wafer (either alone orin assemblies comprising other materials thereon), and semiconductivematerial layers (either alone or in assemblies comprising othermaterials). The term “substrate” refers to any supporting structure,including, but not limited to, the semiconductive substrates describedabove. A first capacitor electrode 16 is formed over substrate 12.Exemplary materials include conductively doped polysilicon or TiN. Anexemplary thickness for layer 16 is from 100 Angstroms to 1500Angstroms.

A first layer 18 of a first capacitor dielectric material is formed overfirst capacitor electrode 16. Exemplary and preferred materials includebarium strontium titanate (BST), strontium titanate (ST), strontiumbismuth titanate (SBT), lead lanthanate zirconia titanate (PLTZ), Ta₂O₅,and mixtures thereof. The preferred method of depositing layer 18 is bychemical vapor deposition. Layer 18 as initially formed can be eithercrystalline or amorphous, with an initial amorphous structure beingpreferred and shown in the fabrication of a capacitor dielectric layerin accordance with this aspect of the invention. Regardless, first layer18 of first capacitor dielectric material is preferably subsequentlyannealed at a temperature of at least 300° C. for a time periodsufficient to achieve a selected crystalline structure intended todensify and facilitate capacitive properties of such material (FIG. 2).Exemplary anneal conditions include a temperature range of from about300° C. to about 1200° C. at a pressure of from about 2 mTorr to about 5atm for a treatment time of anywhere from about 1 minute to 2 hours.Unfortunately as described above with respect to the prior art, suchannealing can cause sufficient recrystallization to form singular grainsat various locations throughout layer 18 having grain boundaries whichextend from one surface of the layer to the other, as shown.

Referring to FIG. 3, a second layer 20 of the same first capacitordielectric material of layer 18 is formed on first layer 18 after thepreferred layer 18 annealing. Second layer 20 is also preferablychemical vapor deposited, and can initially be formed to be amorphous orcrystalline. Preferably, it is initially formed to be amorphous asshown. Further, the thickness of first layer 18 of the first material ispreferably chosen to be from about 10% to about 90% of the finishedcombined thickness of first layer 18 and second layer 20. An exemplarythickness range for the combination of layers 18 and 20 is from 60Angstroms to 1000 Angstroms. By way of example only where the materialof layers 18 and 20 comprises BST, an example thickness for each layer18 and 20 is 150 Angstroms.

Referring to FIG. 4, a second capacitor electrode 22 is formed oversecond layer 20 of the first capacitor dielectric material. An exemplarythickness range for electrode 22 is from 100 Angstroms to 2500Angstroms. Further, diffusion barrier layers, if desired, can bepositioned anywhere intermediate the composite of layers 18 and 20, andfirst electrode 16 and second electrode 22. Regardless, it is mostpreferable that second layer 20 of the first material not be exposed toa temperature of 500° C. or greater before deposition of any subsequentlayer thereover. In certain instances, exposure to such temperature fora sufficient period of time could cause complete crystal realignmentrelative to the composite layer of layers 18 and 20, and undesirablyform grain boundaries which extend from the base of layer 18 clearthrough to the top of layer 20.

Electrode layer 22 and/or any intervening diffusion barrier or otherlayer provided over layer 20 are chosen and deposited in such a way thata degree of desired stress (either tensile or compressive) will beimparted into layer 20, either during formation/deposition orsubsequently such as when it is heated. Such stress can be impartedinherently by the electrode material during its deposition, or bychoosing deposition/forming conditions that themselves impart a desiredstress. For example, selection of temperature and pressure conditionsduring deposition/formation of the electrode layer can be selected toimpart a desired stress regardless of the electrode material beingdeposited. Alternately, the material can be chosen relative to thesecond capacitor dielectric layer to impart a desired tensile orcompressive stress. Such example materials for use with the preferredtitanates and pentoxides capacitor dielectric layers include TiN_(x),WN_(x), TaN_(x), PtRh_(x), PtRu_(x), PtIr_(x), and mixtures thereof.Further alternately, and by way of example only, the second capacitorelectrode material could be doped with a conductivity enhancing impurityduring its formation chosen to achieve a selected stress on the secondlayer of the capacitor dielectric layer.

Regardless, such stress can largely prevent complete recrystallizationof the same material of layers 18 and 20. Exemplary dedicated annealconditions include temperatures ranging from 500° C. to 1000° C., andpressures ranging from 50 mTorr to 50 atmospheres. Accordingly, layer 20is preferably ultimately annealed either with a dedicated anneal step orin conjunction with other wafer processing to render it substantiallycrystalline in its finished composition. Regardless, the preferredcapacitor construction will comprise a pair of capacitor electrodeshaving capacitor dielectric material therebetween comprising a compositeof two immediately juxtaposed and contacting, yet discrete, layers ofthe same capacitor dielectric material, as shown.

Accordingly in the above-described preferred embodiment, first layer 18of the capacitor dielectric layer material is essentially provided witha selected finished crystalline structure prior to formation of secondlayer 20 thereon. Such is achieved by the crystallization orrecrystallization anneal immediately prior to formation of layer 20.Also in the preferred embodiment, the final composition of second layer20 of the first material is also desirably formed to be crystalline,although alternately such could remain amorphous if so initiallydeposited. In the preferred embodiment for a capacitor dielectric layerwhere both of layers 18 and 20 are crystalline in their final form, aninterface line 19 essentially forms therebetween where such discretelayers contact (FIG. 5). Interface line 19 is characterized by aperceptible change in crystallinity from one layer to the other, such asshown or evidenced in this example by a substantial lateral shift ordisplacement in grain boundaries from one layer to the other.

In accordance with another implementation of the invention, first layer18 can comprise a first titanate compound and second layer 20 cancomprise a different second titanate compound. In accordance with stillanother implementation of the invention, first layer 18 can comprise onecapacitor dielectric layer material and second layer 20 can compriseanother different capacitor dielectric layer material, with one of thematerials comprising a titanate compound and the other comprising Ta₂O₅.By way of example only, example titanate compounds are those referred toabove.

Fluorine or other grain boundary passivation treatments can also beconducted relative to the first and second layers of materialintermediate or after such layers have been deposited. Example suchtreatments are described in our U.S. Pat. No. 5,665,611 and referencescited therein.

In compliance with the statute, the invention has been described inlanguage more or less specific as to structural and methodical features.It is to be understood, however, that the invention is not limited tothe specific features shown and described, since the means hereindisclosed comprise preferred forms of putting the invention into effect.The invention is, therefore, claimed in any of its forms ormodifications within the proper scope of the appended claimsappropriately interpreted in accordance with the doctrine ofequivalents.

1-45. (canceled)
 46. A semiconductor construction comprising: a first conductive layer over a substrate; a dielectric material over the first conductive layer, the dielectric material comprising: a first layer having a chemical composition; a second layer having an identical chemical composition relative to the first layer, the second layer being on and in direct physical contact with the first layer; and a perceptible interface between the first and second layers, the perceptible interface being characterized by a perceptible shift in crystallinity from the first layer to the second layer due to a lateral shift in grain boundaries from one layer to the next that occurs at the interface.
 47. The semiconductor construction of claim 46 further comprising a second conductive layer over the dielectric layer.
 48. The semiconductor construction of claim 47 wherein the second conductive layer comprises at least one material selected from the group consisting of TiN_(x), WN_(x), PtRh_(x), PtRu_(x), and PtIr_(x).
 49. The semiconductor construction of claim 47 wherein the second conductive layer is on and in direct physical contact with the insulative material.
 50. The semiconductor construction of claim 46 wherein the first conductive layer comprises at least one of TiN and conductively doped polysilicon.
 51. The semiconductor construction of claim 46 wherein the chemical composition comprises at least one titanate compound.
 52. The semiconductor construction of claim 51 wherein the at least one titanate compound is selected from the group consisting of strontium titanate compounds, strontium bismuth titanate compounds, lead lanthanate zirconia titanate compounds; and barium strontium titanate compounds.
 53. The semiconductor construction of claim 46 wherein the chemical composition comprises Ta₂O₅.
 54. The semiconductor construction of claim 46 wherein the first layer has a thickness of from 10% to 90% of a combined thickness of the first and second layers.
 55. The semiconductor construction of claim 46 wherein the first layer is on and in direct physical contact with the first conductive layer. 